MX2007011278A - Disproportionation of hydridosiloxanes and crosslinked polysiloxane network derived therefrom. - Google Patents
Disproportionation of hydridosiloxanes and crosslinked polysiloxane network derived therefrom.Info
- Publication number
- MX2007011278A MX2007011278A MX2007011278A MX2007011278A MX2007011278A MX 2007011278 A MX2007011278 A MX 2007011278A MX 2007011278 A MX2007011278 A MX 2007011278A MX 2007011278 A MX2007011278 A MX 2007011278A MX 2007011278 A MX2007011278 A MX 2007011278A
- Authority
- MX
- Mexico
- Prior art keywords
- carbon atoms
- radical
- monovalent
- integer
- siloxane
- Prior art date
Links
- -1 hydridosiloxanes Chemical class 0.000 title claims abstract description 165
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 31
- 238000007323 disproportionation reaction Methods 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 37
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 76
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical group FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910008051 Si-OH Inorganic materials 0.000 claims description 2
- 229910006358 Si—OH Inorganic materials 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 abstract description 10
- 125000001424 substituent group Chemical group 0.000 abstract description 6
- 150000003254 radicals Chemical class 0.000 description 34
- 239000000047 product Substances 0.000 description 16
- 125000000524 functional group Chemical group 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 3
- 239000002879 Lewis base Substances 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 150000007527 lewis bases Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Chemical class 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 125000004775 chlorodifluoromethyl group Chemical group FC(F)(Cl)* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000001283 organosilanols Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- UQMGAWUIVYDWBP-UHFFFAOYSA-N silyl acetate Chemical class CC(=O)O[SiH3] UQMGAWUIVYDWBP-UHFFFAOYSA-N 0.000 description 1
- 239000008259 solid foam Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/10—Equilibration processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Disclosed is a crosslinked polysiloxane network comprising both residual Si-H linkages and a Lewis acid catalyst, wherein the network is derived from a linear hydridosiloxane, a branched hydridosiloxane, a cyclic hydridosiloxane or a mixture of a linear hydridosiloxane or branched hydridosiloxane and a cyclic hydridosiloxane. Disclosed also is a method to produce the crosslinked polysiloxane network, alternatively accompanied by a silane with aliphatic, aromatic, or cycloaliphatic substituents by reacting in the presence of an effective amount of a Lewis acid catalyst a linear hydridosiloxane, a branched hydridosiloxane, a cyclic hydridosiloxane or a mixture of a linear hydridosiloxane or branched hydridosiloxane and a cyclic hydridosiloxane.
Description
DEPRESSION OF HYDRIDOSILOXANES AND POLYSYLLOX OR RETICULATED NETWORK DERIVED FROM IT
BACKGROUND OF THE INVENTION The present invention relates to a disproportionation of hydrido siloxanes to produce a product mixture comprising a network of cross-linked polysiloxane. The invention also relates to a network of crosslinked polysiloxane produced thereby. In some particular embodiments, the invention further relates to a product mixture further comprising a mono-substituted silane of the structure RSiH3, wherein R is an aliphatic, cycloaliphatic or aromatic group. The polycondensation reaction of organofunctional silanes or siloxanes such as alkoxysilanes, acetoxysilanes, aminosilanes with silanol-terminated siloxanes can be used for the formation of siloxane networks by a crosslinking process. Many such processes require the presence of a catalyst such as protic acids, Lewis acids, organic and inorganic bases, metal salts or organometallic compounds. (See, for example (a) "The Siloxane Bond" Ed. Voronkov, MG, Mileshkevich, VP, Yuzhelevskii, Yu.A. Consultant Bureau, New York and London, 1978 and (b) Noli,. "Chemistry and Technology of Silicones ", Academia Press, New York, 1968).
It is well known in silicon chemistry that half organoleanol will react with a hydrogen atom directly bonded to a silicon (organohydrosilane) to produce a hydrogen molecule and the silicon-oxygen bond, (see, for example, "Silicon in Organic, Organometallie and Polymer Chemistry "Michael A. Brook, John Wiley &Sons, Inc., New York, Chichester, Weinheim, Brisbane, Singapore, Toronto, 2000). Although the uncatalyzed reaction will be activated at elevated temperatures, it is widely known that this reaction will be readily activated in the presence of a transition metal catalyst, especially noble metal catalysts such as those comprising platinum, palladium, etc., a base catalyst such as an alkali metal hydroxide, amine, etc., or a Lewis acid catalyst, such as a tin compound, etc. Recently, organoboron compounds have been reported to be extremely effective catalysts for the reaction between organohydridosilanes and organosilanols (WO 01/74938 Al), which lead to the formation of a crosslinked network. Unfortunately, the byproduct of this process is highly dangerous reactive hydrogen. The aliphatic, cycloaliphatic and aromatic silanes comprising a Si-H functionality are typically produced by the reduction of chlorosilanes. These Si-H functional silanes find their use in electronic materials, semiconductors, integrated circuits, as useful intermediates for a variety of different products, and similar applications. This synthesis reaction is, however, very risky since the reactants are very difficult to handle. There is a constant need to develop new reactions that will improve the versatility and safety of the processes used to produce polysiloxane networks and also aliphatic, cycloaliphatic and aromatic silanes.
BRIEF DESCRIPTION OF THE INVENTION In the present invention, it has been discovered unexpectedly by reacting a linear hydrido siloxane, a branched hydrido siloxane, a cyclic hydrido siloxane or a mixture of a linear or branched hydrido siloxane with a cyclic hydrido siloxane in the presence of an effective Lewis acid produces a network of crosslinked polysiloxane. It has also been found that the reaction can produce a silane with aliphatic, aromatic or cycloaliphatic substituents. The method described herein is a safe and convenient process for producing a network of crosslinked polysiloxane and also typically silanes with aliphatic, aromatic and cycloaliphatic substituents, in contrast to the methods described in the prior art which are typically costly and use hazardous materials. In one embodiment, the invention relates to a method for producing a network of crosslinked polysiloxane; the method comprises the step of reacting in the presence of an effective amount of a Lewis acid catalyst; either a linear or branched hydrido siloxane represented by structure (I): wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a monovalent aromatic radical of 3 to 40 carbon atoms , or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'a' is an integer between 2 and 10000 and 'b' is an integer between 0 and 10000; or b) a cyclic hydrido siloxane represented by structure (II): (II) (SiHR10) c (SIR2R30) d wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a radical monovalent aromatic of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'c' is an integer between 2 and 10 and 'd' is an integer between 0 and 8, with the proviso that the sum of 'c1 +' d 'is in the range from 3 to 10; or c) a mixture of at least one linear or branched siloxane of the formula (I) and at least one cyclic siloxane of the formula (II). In another embodiment, the invention relates to a method for producing (i) a network of crosslinked polysiloxane and
(ii) a silane of formula R1SiH3, the method comprises the step of reacting in the presence of an effective amount of a Lewis acid catalyst; either a linear or branched hydrido siloxane represented by structure (I): (I) (SiHR10) a (SiR2R30) b wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a monovalent aromatic radical of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'a' is an integer between 2 and 10000 and 'b1 is an integer between 0 and 10000; or b) a cyclic hydrido siloxane represented by structure (II): (II) (SiHR10) c (SiR2R30) d wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a radical monovalent aromatic of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'c1 is an integer between 2 and 10 and' d 'is an integer between 0 and 8, with the proviso that the sum of' c '+' d 'is in the range from 3 to 10; or c) a mixture of at least one linear or branched siloxane of the formula (I) and at least one cyclic siloxane of the formula (II). In a further embodiment, the invention relates to a cross-linked polysiloxane network comprising both residual Si-H bonds and a Lewis acid catalyst; wherein the crosslinked network is derived from a) a linear or branched hydrido siloxane represented by structure (I): (I) (SiHR10) a (SiR2R30) b wherein R2 and R3 are, independently in each case, a radical monovalent aliphatic of 1 to 20 carbon atoms, a monovalent aromatic radical of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'a' is an integer between 2 and 10000 and 'b' is an integer between 0 and 10000; or b) a cyclic hydrido siloxane represented by structure (II): (II) (SiHR10) c (SiR2R30) d wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a radical monovalent aromatic of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'c' is an integer between 2 and 10 and 'd' is an integer between 0 and 8, with the proviso that the sum of 'c' + 'd' is in the range from 3 to 10; or c) a mixture of at least one linear or branched siloxane of the formula (I) and at least one cyclic siloxane of the formula (II). Various other features, aspects and advantages of the present invention will become more apparent with reference to the following description and appended claims.
DETAILED DESCRIPTION OF THE INVENTION In the following specification and the claims that follow it, reference will be made to a number of terms that must be defined with the following meanings. The singular forms of "a" "an" and "the" include plural referents unless the context clearly dictates otherwise.
As used herein, the term "aliphatic radical" refers to an organic radical having a valence of at least one that comprises a linear or branched arrangement of atoms that is not cyclic. Aliphatic radicals are defined to comprise from one to 40 carbon atoms. The atom arrangement comprising the aliphatic radical can be composed exclusively of carbon and hydrogen or can include heteroatoms, such as nitrogen, sulfur, silicon, selenium and oxygen, as long as the heteroatoms do not interfere with the disproportionation reaction, for example, to the deactivate the catalyst totally or partially. For convenience, the term "aliphatic radical" is defined herein to encompass, as part of the "linear or branched arrangement of atoms that is not cyclic" a broad range of functional groups such as alkyl groups, alkenyl groups, alkylino groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups , nitro groups and the like, as long as the functional group does not interfere with the disproportionation reaction, for example, by deactivating the catalyst totally or completely. For example, the 4-methylpent-1-yl radical is an aliphatic radical of 6 carbon atoms comprising a methyl group, the methyl group is a functional group which is an alkyl group. An aliphatic radical can be a haloalkyl group comprising one or more halogen atoms, which may be the same or different. Halogen atoms include, for example, fluorine, chlorine, bromine and iodine. Aliphatic radicals comprising one or more halogen atoms include the halide alkyl trifluoromethyl, 1,1,1-trifluoropropyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoroisopropylidene; chloromethyl; difluorovinylidene; trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene (for example, -CH2CHBrCH2-) and the like. Suitable aliphatic groups also include aliphatic silyl groups of the formula R'-Si- (R) 3, wherein R is a monovalent aliphatic radical of 1 to 20 carbon atoms or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms, and R1 is an aliphatic radical of 2 to 10 carbon atoms. By way of a further example, an aliphatic radical of 1 to 10 carbon atoms contains at least one, but not more than 10, carbon atoms. A methyl group (i.e., CH3-) is an example of an aliphatic radical of 1 carbon atom. A decyl group (ie CH3 (CH2)? 0-) is an example of an aliphatic radical of 10 carbon atoms. As used herein, the term "aromatic radical" refers to an arrangement of atoms having a valence of at least one, which comprises at least one aromatic group comprising from 3 to 40 carbon atoms. The arrangement of atoms has a valence of at least one comprising at least one aromatic group can include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or can be composed exclusively of carbon and hydrogen. As used herein, the term "aromatic radical" includes, but is not limited to, phenyl, pyridyl, furanyl, thienyl, phenylene and biphenyl radicals, so long as the aromatic radicals do not interfere with the disproportionation reaction, example, by deactivating the catalyst completely or partially. The aromatic radical can also include non-aromatic components. For example, a benzyl group is an aromatic radical comprising a phenyl ring (the aromatic group) and a methylene group (the non-aromatic component). Similarly, a tetrahydronaphthyl radical is an aromatic radical comprising an aromatic group (C6H3) combined with a non-aromatic component - (CH2) 4-. For convenience, the term "aromatic radical" is defined herein to encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkylino groups, haloalkyl groups, haloaromatic groups, conjugated dienyl groups, alcohol groups, ether groups, groups aldehyde, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups and the like, as long as the functional group does not interfere with the disproportionation reaction, example, by deactivating the catalyst partially or completely. For example, the 4-methylphenyl radical is an aromatic radical of 7 carbon atoms comprising a methyl group, the methyl group is a functional group which is an alkyl group. Aromatic radicals include halogenated aromatic radicals, such as trifluoromethylphenyl, hexafluoroisopropylidenebis (4-phen-1-yloxy) (ie, OphC (CF3) 2PhO-, chloromethylphenyl; 3-trifluorovinyl-2-thienyl; 3-trichloromethylphen-1-yl (ie, 3-CCl3Ph-), 4- (3-bromoprop-1-yl) phen-1-yl (ie, BrCH2CH2CHPh-), and the like The term "an aromatic radical of 3 to 10 carbon atoms "includes aromatic radicals containing at least three, but not more than 10 carbon atoms.The aromatic radical 1-imidazolyl (C3H2N2-) represents an aromatic radical of 3 carbon atoms.The benzyl radical (C7H8-) represents a aromatic radical of 7 carbon atoms As used herein, the term "cycloaliphatic radical" refers to a radical having a valence of at least one, and comprising an arrangement of atoms that is cyclic but not It is aromatic.The cycloaliphatic radical can comprise from 3 to 40 atoms of carbon As defined herein, a "cycloaliphatic radical" does not contain an aromatic group. A "cycloaliphatic radical" may comprise one or more non-cyclic components. For example, a cyclohexylmethyl group (C6H11CH2-) is a cycloaliphatic radical that comprises a cyclohexyl ring (the arrangement of atoms that is cyclic, but not aromatic) and a methylene group (the non-cyclic component). The cycloaliphatic radical can be exclusively composed of carbon and hydrogen or can include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, so long as the heteroatoms do not interfere with the disproportionation reaction, for example, by deactivating the catalyst in whole or in part . For convenience, the term "cycloaliphatic radical" is defined herein to encompass a wide range of functional groups, such as alkyl groups, alkenyl groups, alkylino groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups and the like, as long as the functional group does not interfere with the disproportionation reaction, for example, by deactivating the catalyst totally or completely. For example, the 4-methylcycloyl en-1-yl radical is a cycloaliphatic radical of 6 carbon atoms comprising a methyl group, the methyl group is a functional group which is an alkyl group. A cycloaliphatic radical may comprise one or more halogen atoms which may be the same or different. Halogen atoms include, for example, fluorine, chlorine, bromine and iodine. Cycloaliphatic radicals comprising one or more halogen atoms include 2-trifluoromethylenecyclohex-1-yl, 4-bromodifluoromethyl-cyclooct-1-yl, 2-chlorodifluoromethyl-cyclohex-1-yl, hexafluoroisopropylidene-2,2-bis (cyclohex-4-yl) ( that is, -C6H? 0C (CF3) 2C6H? o-), 2-chloromethylcyclohex-1-yl; 3-difluoromethylenecyclohex-1-yl; 4-trichloromethylcyclohex-1-yloxy, 4-bromo-dichloromethyl-cyclohex-1-ylthio, 2-bromoethyl-cyclopen-1-yl, 2-bromopropyl-cyclohex-1-yloxy (for example, CH3CHBrCH2C6H-0-), and the like. Suitable cycloaliphatic groups also include cycloaliphatic silyl groups of the formula -R'-Si- (R) 3, wherein R is a monovalent aliphatic radical of 1 to 20 carbon atoms or a cycloaliphatic radical of 3 to 40 carbon atoms, and R 'is a cycloaliphatic radical of 2 to 10 carbon atoms. The term "a cycloaliphatic radical of 3 to 10 carbon atoms" includes cycloaliphatic radicals containing at least three but not more than 10 carbon atoms. The cycloaliphatic radical 2-tetrahydrofuranyl (C4H70-) represents a cycloaliphatic radical of 4 carbon atoms. The cyclohexylmethyl radical (C6H1: LCH2-) represents a cycloaliphatic radical of 7 carbon atoms.
This invention relates to an unexpected discovery of a method for producing a mixture comprising a cross-linked polysiloxane network; the method comprises the step of reacting in the presence of an effective amount of a Lewis acid catalyst; either a linear or branched hydrido siloxane represented by structure (I): wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a monovalent aromatic radical of 3 to 40 carbon atoms , or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'a' is an integer between 2 and 10000 and 'b' is an integer between 0 and 10000; or b) a cyclic hydrido siloxane represented by structure (II) (II) (SiHR10) c (SiR2R30) d wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, an aromatic radical monovalent of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and • c 'is an integer between 2 and 10 and' d 'is an integer between 0 and 8, with the proviso that the sum of' c '+' d 'is in the range from 3 to 10; or c) a mixture of at least one linear or branched siloxane of the formula (I) and at least one cyclic siloxane of the formula (II). Typical groups of R2 and R3 include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, decyl, dodecyl, phenyl, naphthyl, benzyl, cyclohexyl, or methylcyclohexyl. In a typical embodiment of the invention, when the siloxane reactant chosen is a linear or branched siloxane, all the Si-H bonds are internal and the terminal groups do not contain any Si-H bond. A typical siloxane that can be used in the invention is tetramethylcyclotetrasiloxane ((SiMe (H) O) 4; D4H; CAS # 2370-88-9). In some particular embodiments the product mixture also comprises a silane of formula RxSiH3. In a particular embodiment, the product mixture also comprises CH3SiH3. The reaction is achieved in the presence of an appropriate catalyst. For this reaction, the catalyst is preferably a Lewis acid catalyst. In some embodiments, the catalysts used for the reaction comprise Lewis acid catalysts of the formula (III) MR4xXy (III) wherein M is B, Al, Ga, In or Ti; each R4 is independently the same or different and represents a monovalent aromatic radical, such monovalent aromatic radicals preferably comprise at least one electron withdrawing substituent; X is a halogen atom; 'x' is 1, 2 or 3, and 'y' is 0, 1 or 2, with the proviso that 'x' + 'y1 = 3. In other embodiments, the catalysts used for the reaction comprise carboxylic acid catalysts. Lewis of formula (IV) BR4xXy (IV) wherein each R4 is independent the same or different and represents a monovalent aromatic radical, such monovalent aromatic radicals preferably comprise at least one electron withdrawing substituent; X is a halogen atom; 'x' is 1, 2 or 3, and 'y' is 0, 1 or 2, with the proviso that 'x' + 'y' = 3. Typical examples of such Lewis acid catalysts include, but are not limit to:
t (C5F4) (C6F5) 2B. (CsF4) 3B; (C6F5) BF2. BFíCß j),. BÍCiF?; B (C6HS) (C6F5) 2. BOßíC?); BC1 (C6FS) 2; [C6H4 (.CF3)] 3B. (c6H4 (p-CF3)) 3B (C6H2-2.4.6- (CF3) 3) 3B, (C6H2-3.4.5- (CF3) 3) 3B,
In a particular embodiment, the Lewis acid catalyst is tris (pentaflurophenyl) borate (B (C6F5) 3; CAS # 1109-15-5). The catalyst is typically used in an amount in a range from about 1 ppm by weight to about 10000 ppm by weight, more preferably from about 10 ppm by weight to about 2000 ppm by weight, and most preferably from about 25 ppm by weight to about 1000 ppm by weight. The reaction can be carried out without solvent or in the presence of one or a mixture of more than one solvent. The solvent, when present, can provide an increased capacity to control the viscosity, reaction rate and exothermicity of the process. When present, the preferred solvents comprise aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, as well as oligomeric cyclic dioganosiloxanes that do not comprise Si-H bonds. The reaction can be carried out at room temperature or can be carried out at higher temperatures depending on such illustrative factors as the chemical structures of the reactants and catalysts, catalyst concentration and the presence and type of solvent. A typical reaction mixture is prepared by combining a reactant comprising at least one linear or branched siloxane or at least one cyclic siloxane or a mixture thereof, and a Lewis acid catalyst in the presence of an optional solvent. In one aspect of the invention, the shelf life of such a formulation can optionally be extended by the addition of a stabilizing agent. Typical stabilizing agents are Lewis bases which can form compounds with a Lewis acid catalyst. Illustrative Lewis bases include, but are not limited to, ammonia, primary amines, secondary amines, tertiary amines and organophosphines. The reaction may be allowed to continue until the catalyst is substantially or completely trapped in the crosslinked polysiloxane network, rendering it inaccessible to the reactant, as shown by a decreasing rate of product generation. In an alternate embodiment, an extinguishing agent may optionally be added at any given time to stop the reaction. The extinguishing agents, when used, can be chosen from the group of Lewis bases which can form concentrated compounds with the Lewis acid catalysts. Typical extinguishing agents include, but are not limited to, ammonia, primary amines, secondary amines, tertiary amines, organophosphines and basic metal oxides, illustrative examples of which comprise calcium oxide, magnesium oxide and the like. The products of the reaction comprise a cross-linked polysiloxane network. The crosslinked polysiloxane network typically comprises a Lewis acid catalyst substantially or completely trapped therein. The resulting product can be isolated from the reaction mixture and purified, if desired, by typical methods known to those skilled in the art, or can be used without isolation. The crosslinked polysiloxane network finds its use in many applications, including, but not limited to, siloxane elastomers, siloxane coatings, encapsulants, sealants, insulating materials and cosmetic products. The product of the crosslinked polysiloxane network can still comprise significant amounts of available Si-H bonds for further reaction. It is within the scope of the invention to subject the product of the cross-linked polysiloxane network to an additional reaction with a suitable reagent, and optionally a catalyst, to convert less than 100% of the remaining residual Si-H bonds to another link comprising at least one of Si-OH, Si-OR, Si-R or Si-OAr, wherein R is a monovalent aliphatic radical of 1 to 20 carbon atoms, an aliphatic silyl radical, a cycloaliphatic silyl radical, an monovalent aromatic radical of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms, and wherein "Ar" is a monovalent aromatic group of 3 to 40 carbon atoms. In certain embodiments, another product of the reaction is a mono-substituted silane compound represented by the formula R1SiH3, wherein R1 is a monovalent aliphatic radical, a monovalent aromatic radical, or a monovalent cycloaliphatic radical. Illustrative R1 groups in the silane include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, decyl, dodecyl, 1,1-trifluoropropyl, phenyl, naphthyl, benzyl, cyclohexyl or methylcyclohexyl groups. The physical state of the silane compound depends on such factors as the substituent on the silicon atom; and the temperature, pressure and other predominant reaction conditions. This product can be isolated and purified, if desired, by conventional methods known to those skilled in the art. For example, the silane product, when produced as a gas, can be condensed as such in a suitable container that can optionally be cooled to prevent evaporation or can be condensed in a solvent that can optionally be cooled to prevent evaporation. Methods for collecting and storing silane products are known to those skilled in the art and can be employed in the method of the present invention. The silane compounds described herein are useful in various applications, including, but not limited to, electronic applications in many processes such as chemical vapor deposition. Without further elaboration, it is considered that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following examples are included to provide additional guidance for those skilled in the art for practicing the claimed invention. The examples provided are simply representative of the work that contributes to the teaching of this application. Accordingly, these examples are not intended to limit the invention, as defined in the appended claims, in any way.
EXAMPLES In the following examples tetramethylcyclotetrasiloxane [(SiMe (H) 0) 4; DH) and a linear siloxane copolymer comprising parts of Si-H were obtained from GE Silicones, Waterford, New York. The catalyst used was tris (pentafluorophenyl) borate obtained from Aldrich Chemical Co., Milwaukee, Wisconsin. The analysis of any gaseous product was carried out using gas chromatography coupled with mass spectrometer (GC / MS). The cross-linked polysiloxane networks were analyzed by 29SiNMR spectroscopy in the solid state.
EXAMPLE 1 In a 20 milliliter glass flask (ml) equipped with a magnetic stir bar, 5 grams (g) (0.024 moles) of D4H were mixed with 0.0025 g (4.88 x 10"6 moles) of tris (pentafluorophenyl) borate.The bottle was sealed with a plastic cap and the reaction mixture was stirred magnetically at room temperature.The reaction mixture increased its viscosity rapidly and then solidified after 5 minutes to form an elastic gel. to form within the gel in the next 5 minutes, which led to an increase in pressure in the bottle.In the next few minutes, the elastic gel was transformed into a solid and brittle foam. The GC formation of the released gas showed the formation of MeSiH3 and less than 1% of Me2SiH2, and the analysis of 29SiNMR in solid state confirmed the formation of gas. quotas of MeSi03 / 2 and MeSiH20? / 2.
EXAMPLE 2 In a 20 milliliter (ml) glass scintillation flask equipped with a magnetic stir bar, 5 grams (g) of linear siloxane copolymer comprising about 50 mol% of dimethylsiloxane structural units and 50% was mixed. of moles of structural units of methylhydridosiloxane with 0.005 g (9.76 x 10"6 moles) of tris (pentafluorophenyl) borate.The bottle was sealed with a plastic lid and the reaction mixture was stirred magnetically at room temperature. It increased in viscosity quickly and then solidified after 5 minutes to form an elastic gel.Gas bubbles began to form inside the gel in the next 5 minutes.In the following few minutes, the elastic gel was transformed into a solid foam. At this point, it was observed that the velocity of the gas formation had decreased significantly The GC / MS analysis of the gas released showed the formation of MeSiH 3 and less than 1% of Me2SiH2. Although the invention has been illustrated and described in typical embodiments, it is not intended to be limited to the details shown, since various modifications and substitutions may be made without departing in any way from the spirit of the present invention. As such, modifications and additional equivalents of the invention described herein may be made by persons skilled in the art using no more than one experimentation routine, and all such modifications and equivalents are considered to be within the spirit and scope of the invention. the invention as defined by the following claims. All patents and published articles cited herein are incorporated herein by reference.
Claims (25)
- CLAIMS 1. A method for producing a network of crosslinked polysiloxane; the method comprises the step of reacting in the presence of an effective amount of a Lewis acid catalyst: either a linear or branched hydrido siloxane represented by structure (I): (I) (SiHR10) a (SiR2R30) b wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a monovalent aromatic radical of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'a1 is an integer between 2 and 10000 and' b1 is an integer between 0 and 10000; or b) a cyclic hydrido siloxane represented by structure (II): (II) (SiHR10) c (SiR2R30) d wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a radical monovalent aromatic of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'c1 is an integer between 2 and 10 and' d 'is an integer between 0 and 8, with the proviso that the sum of' c '+' d 'is in the range from 3 to 10; or c) a mixture of at least one linear or branched siloxane of the formula (I) and at least one cyclic siloxane of the formula (II).
- 2. The method of claim 1, wherein a silane of the formula R1SiH3 is also produced, wherein R1 is selected from the group consisting of hydrogen, a monovalent aliphatic radical of 1 to 20 carbon atoms, a monovalent aromatic radical of 3 to 40 carbon atoms, and a monovalent cycloaliphatic radical of 3 to 40 carbon atoms.
- 3. The method of claim 2, wherein the silane is isolated from the reaction mixture.
- The method of claim 2, wherein the silane comprises a methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, 1,1-trifluoropropyl, phenyl, naphthyl group , benzyl, cyclohexyl, or methylcyclohexyl.
- The method of claim 1, wherein R2 and R3 are, independently in each case, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, 1,1-trifluoropropyl phenyl, naphthyl, benzyl, cyclohexyl, or methylcyclohexyl.
- 6. The method of claim 1, wherein the cross-linked polysiloxane network is isolated from the reaction mixture.
- The method of claim 1, wherein the catalyst is used in an amount in a range from about 1 ppm to about 10000 ppm by weight.
- The method of claim 1, wherein the catalyst comprises boron.
- 9. The method of claim 8, wherein the catalyst is tris (pentafluorophenyl) borate.
- 10. The method of claim 1, wherein the reaction is carried out in the presence of a solvent.
- The method of claim 1, wherein the reaction is carried out at a temperature in a range from about 0 ° C to about 150 ° C.
- 12. The method of claim 1, wherein the reaction is quenched.
- 13. A network of crosslinked polysiloxane having residual Si-H bonds produced by the method of claim 1.
- 14. A method for producing (i) a network of cross-linked polysiloxane and (ii) a silane of formula R1SiH3; the method comprises the step of reacting in the presence of an effective amount of a Lewis acid catalyst: either (a) a linear or branched hydrido siloxane represented by structure (I): (I) (SiHR10) a (SiR2R30 ) b wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a monovalent aromatic radical of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'a' is an integer between 2 and 10000 and 'b' is an integer between 0 and 10000; or b) a cyclic hydrido siloxane represented by structure (II): (II) (SiHR10) c (SiR2R30) d wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a radical monovalent aromatic of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'c1 is an integer between 2 and 10 and' d1 is an integer between 0 and 8, with the proviso that the sum of 'c' + 'd' is in the range spanning from 3 to 10; or c) a mixture of at least one linear or branched siloxane of the formula (I) and at least one cyclic siloxane of the formula (II).
- 15. The method of claim 14, wherein R2 and R3 are, independently in each case, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, 1,1-trifluoropropyl. , phenyl, naphthyl, benzyl, cyclohexyl, or methylcyclohexyl.
- 16. The method of claim 14, wherein the crosslinked polysiloxane network is isolated from the reaction mixture.
- 17. The method of claim 14, wherein the silane is isolated from the reaction mixture.
- 18. The method of claim 14, wherein the Lewis acid catalyst comprising boron is tris (pentafluorophenyl) borate.
- The method of claim 14, wherein the reaction is carried out at a temperature in a range from about 0 ° C to about 150 ° C.
- The method of claim 14, wherein the reaction is carried out in the presence of a solvent.
- 21. A method for producing (i) a network of cross-linked polysiloxane and (ii) a silane of formula R1SiH3, the method comprising the step of reacting, at room temperature, in the presence of about 100 ppm by weight of tris catalyst ( pentafluorophenyl) borate, and optionally in the presence of a solvent; either a linear or branched hydrido siloxane represented by structure (I): (I) (SiHR10) a (SiR2R30) b wherein R2 and R3 are, independently in each case, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, phenyl, naphthyl, benzyl, cyclohexyl, or methylcyclohexyl; R1 is hydrogen or the same as R2; and 'a' is an integer between 2 and 10000 and 'b' is an integer between 0 and 10000; or b) a cyclic hydrido siloxane represented by structure (II): (II) (SiHR10) c (SiR2R30) d wherein R2 and R3 are, independently in each case, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, phenyl, naphthyl, benzyl, cyclohexyl, or methylcyclohexyl; R1 is hydrogen or the same as R2; and 'c1 is an integer between 2 and 10 and' d 'is an integer between 0 and 8, with the proviso that the sum of • c' + 'd' is in the range from 3 to 10; or c) a mixture of at least one linear or branched siloxane of the formula (I) and at least one cyclic siloxane of the formula (II).
- 22. A cross-linked polysiloxane network comprising both residual Si-H bonds and a Lewis acid catalyst.
- 23. The crosslinked polysiloxane network of claim 22, wherein the crosslinked network is derived from (a) a linear or branched hydrido siloxane represented by structure (I): (I) (SiHR10) a (SiR2R30) b wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a monovalent aromatic radical of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'a' is an integer between 2 and 10000 and 'b' is an integer between 0 and 10000; or b) a cyclic hydrido siloxane represented by structure (II): (II) (SiHR10) c (SiR2R30) d wherein R2 and R3 are, independently in each case, a monovalent aliphatic radical of 1 to 20 carbon atoms, a radical monovalent aromatic of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; R1 is hydrogen or the same as R2; and 'c' is an integer between 2 and 10 and 'd' is an integer between 0 and 8, with the proviso that the sum of 'c' + 'd1 is in the range from 3 to 10; or c) a mixture of at least one linear or branched siloxane of the formula (I) and at least one cyclic siloxane of the formula (II).
- 24. The crosslinked polysiloxane network of claim 22, wherein the Lewis acid catalyst is tris (pentafluorophenyl) borate.
- 25. The crosslinked polysiloxane network of claim 22, wherein less than 100% of the remaining residual Si-H bonds are subsequently converted to another bond comprising at least one Si-OH, Si-OR, Si-R. or Si-OAr, wherein R is a monovalent aliphatic radical of 1 to 20 carbon atoms, an aliphatic radical of silyl, a cycloaliphatic radical of silyl, a monovalent of 3 to 40 carbon atoms, a monovalent aromatic radical of 3 to 40 carbon atoms, or a monovalent cycloaliphatic radical of 3 to 40 carbon atoms; and wherein "Ar" is a monovalent aromatic group of 3 to 40 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/081,070 US20060211836A1 (en) | 2005-03-15 | 2005-03-15 | Disproportionation of hydridosiloxanes and crosslinked polysiloxane network derived therefrom |
| PCT/US2006/008656 WO2006101778A1 (en) | 2005-03-15 | 2006-03-10 | Disproportionation of hydridosiloxanes and crosslinked polysiloxane network derived therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MX2007011278A true MX2007011278A (en) | 2008-03-19 |
Family
ID=36571228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX2007011278A MX2007011278A (en) | 2005-03-15 | 2006-03-10 | Disproportionation of hydridosiloxanes and crosslinked polysiloxane network derived therefrom. |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20060211836A1 (en) |
| EP (1) | EP1861451A1 (en) |
| JP (1) | JP2008537753A (en) |
| KR (1) | KR20070112837A (en) |
| CN (1) | CN101184790A (en) |
| BR (1) | BRPI0609383A2 (en) |
| MX (1) | MX2007011278A (en) |
| RU (1) | RU2007138034A (en) |
| WO (1) | WO2006101778A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8048819B2 (en) * | 2005-06-23 | 2011-11-01 | Momentive Performance Materials Inc. | Cure catalyst, composition, electronic device and associated method |
| DE102007037292A1 (en) | 2007-08-07 | 2009-02-12 | Evonik Goldschmidt Gmbh | Process for the preparation of branched polyorganosiloxanes |
| US9246173B2 (en) | 2012-11-16 | 2016-01-26 | Mitsubishi Chemical Corporation | Process for synthesis of hybrid siloxy derived resins and crosslinked networks therefrom |
| CN103059301B (en) * | 2012-12-11 | 2015-02-25 | 曹坚林 | Phenyl hydrogen-containing reticular silicon resin for LED packaging and preparation method thereof |
| CN103865065B (en) * | 2014-03-26 | 2017-01-04 | 苏州桐力光电股份有限公司 | A kind of preparation method of MT resin |
| US20200207919A1 (en) | 2017-05-23 | 2020-07-02 | Wacker Chemie Ag | Crosslinking of hydridosiloxanes with silicon (ii) compounds |
| CN109134891B (en) * | 2018-08-14 | 2021-07-13 | 山东圣佑高科新材料有限公司 | Preparation method of phenyl organosilicon elastomer |
| JP7637073B2 (en) | 2019-06-04 | 2025-02-27 | ダウ シリコーンズ コーポレーション | Thermally Initiated, Acid-Catalyzed Reaction of Silyl Hydrides with α-β Unsaturated Esters |
| KR20220016899A (en) | 2019-06-04 | 2022-02-10 | 다우 실리콘즈 코포레이션 | Thermally Initiated Acid Catalyzed Reaction of Silyl Hydride with Siloxane |
| KR20220016900A (en) | 2019-06-04 | 2022-02-10 | 다우 실리콘즈 코포레이션 | Bridged incomplete Lewis pairs as thermal triggers for the reaction of Si-H with Si-O-Si |
| US12104019B2 (en) | 2019-06-04 | 2024-10-01 | Dow Silicones Corporation | Bridged frustrated Lewis pairs as thermal trigger for reactions between Si—H and alpha-beta unsaturated esters |
| WO2020247334A1 (en) | 2019-06-04 | 2020-12-10 | Dow Silicones Corporation | Bridged frustrated lewis pairs as thermal trigger for reactions between si-h and si-or |
| KR20220016906A (en) | 2019-06-04 | 2022-02-10 | 다우 실리콘즈 코포레이션 | Thermally initiated acid catalyzed reaction between silyl hydride and silyl ether and/or silanol |
| JP7560490B2 (en) | 2019-06-04 | 2024-10-02 | ダウ シリコーンズ コーポレーション | Bridging Frustrated Lewis Pairs as Thermal Triggers for the Reaction of Si-H with Epoxides |
| WO2021247210A1 (en) | 2020-06-04 | 2021-12-09 | Dow Silicones Corporation | Epoxy-curable silicone release coating composition and methods for its preparation and use |
| CN115124842B (en) * | 2022-07-15 | 2023-10-17 | 东莞市润银实业有限公司 | Wide-temperature-range storage-resistant silicone rubber and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2731485A (en) * | 1949-07-26 | 1956-01-17 | Union Carbide & Carbon Corp | Polysiloxanes produced by the reaction of dialkyldialkoxysilanes in the presence of aluminum or boron halides |
| GB876708A (en) * | 1958-03-28 | 1961-09-06 | Director Of The Agency Of Ind | Process for producing alkylhydrosilanes |
| GB8615862D0 (en) * | 1986-06-28 | 1986-08-06 | Dow Corning Ltd | Making siloxane resins |
| FR2729961B1 (en) * | 1995-01-31 | 1997-04-25 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF A POLYORGANOSILOXANE RESIN, POSSIBLY ALCOXYLATED, BY NON-HYDROLYTIC CONDENSATION |
| US5516867A (en) * | 1995-05-12 | 1996-05-14 | Dow Corning Corporation | Modified hydrogen silsesquioxane resin |
| FR2800380B1 (en) * | 1999-10-29 | 2002-01-18 | Rhodia Chimie Sa | POLYMERIZATION AND / OR CROSSLINKAGE PRIMER OF POLYORGANOSILOXANES WITH CROSSLINKABLE FUNCTIONAL GROUPS, CORRESPONDING COMPOSITIONS AND USES THEREOF |
| FR2806930B1 (en) * | 2000-04-04 | 2002-06-28 | Rhodia Chimie Sa | USE OF A BORON DERIVATIVE AS A THERMOACTIVABLE CATALYST FOR THE POLYMERIZATION AND/OR CROSS-LINKING OF SILICONE BY DEHYDROGENOCONDENSATION |
| US7064173B2 (en) * | 2002-12-30 | 2006-06-20 | General Electric Company | Silicone condensation reaction |
-
2005
- 2005-03-15 US US11/081,070 patent/US20060211836A1/en not_active Abandoned
-
2006
- 2006-03-10 WO PCT/US2006/008656 patent/WO2006101778A1/en not_active Ceased
- 2006-03-10 KR KR1020077022762A patent/KR20070112837A/en not_active Withdrawn
- 2006-03-10 MX MX2007011278A patent/MX2007011278A/en unknown
- 2006-03-10 CN CNA2006800166602A patent/CN101184790A/en active Pending
- 2006-03-10 EP EP06737796A patent/EP1861451A1/en not_active Withdrawn
- 2006-03-10 RU RU2007138034/04A patent/RU2007138034A/en not_active Application Discontinuation
- 2006-03-10 BR BRPI0609383-3A patent/BRPI0609383A2/en not_active Application Discontinuation
- 2006-03-10 JP JP2008501924A patent/JP2008537753A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP1861451A1 (en) | 2007-12-05 |
| JP2008537753A (en) | 2008-09-25 |
| KR20070112837A (en) | 2007-11-27 |
| BRPI0609383A2 (en) | 2010-03-30 |
| CN101184790A (en) | 2008-05-21 |
| WO2006101778A1 (en) | 2006-09-28 |
| RU2007138034A (en) | 2009-04-27 |
| US20060211836A1 (en) | 2006-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| MX2007011278A (en) | Disproportionation of hydridosiloxanes and crosslinked polysiloxane network derived therefrom. | |
| CN102549001B (en) | Carbon dioxide absorbent and method of use thereof | |
| US7064173B2 (en) | Silicone condensation reaction | |
| CA2144639C (en) | Single component inorganic/organic network materials and precursors thereof | |
| JP3474007B2 (en) | Method for producing organofunctional organosiloxane containing organic functional groups | |
| JP3813486B2 (en) | Process for the preparation of aminofunctional organosiloxanes | |
| US9273072B2 (en) | Method for producing organosilicon compounds which have amino groups | |
| CN107207949B (en) | Branched organosiloxanes for use as heat transfer fluids | |
| JPH03170530A (en) | Organopolysiloxane having one branched molecular terminal and blocked by aminoalkyl group, and its preparation | |
| US10336866B2 (en) | Method for producing organosilicon compounds having amino groups | |
| KR20150006833A (en) | Novel, mono-synthesizable, spontaneously water-soluble, substantially voc-free, environmentally friendly (meth)acrylamido-functional siloxanol systems, process for their preparation and use | |
| JPS61263986A (en) | Organic silicon compound | |
| US6399733B1 (en) | Process for preparing a highly pure silicone ladder polymer | |
| JPH04351638A (en) | Hexenylated silicone resin and production thereof | |
| US5939574A (en) | Aminosiloxanes with 4-amino-3,3-dialkylbutyl groups | |
| CN104403104B (en) | A kind of titaniferous condensed type catalyst, its preparation method and application | |
| KR20190058653A (en) | Manufacturing method of hydridosilane | |
| CN1371382A (en) | Method for preparation of aminopropyl or aminoalkyl functional polyalkyl or aryl siloxanes | |
| JP2009500321A (en) | Synthesis method of diorganosilane by disproportionation of hydridosilane | |
| JP2001335585A (en) | Poly (aminoalkylsiloxane) | |
| TW201819393A (en) | Polymer with alternating phenylene and silicon siloxane framework, and method for preparing its precursor for improving the compatibility of inorganic silicon-based flame retardant and the polymer substrate, so as to prevent the properties of polymer material and the processing performance from being affected | |
| JPH07224072A (en) | Method for producing 1,1,3,3-tetramethyl-1,3-dihydroxydisiloxane | |
| CN101228209A (en) | Process for the synthesis of diorganosilanes by disproportionation of hydrosiloxanes | |
| KR20250110277A (en) | Composition comprising aminoalkylalkoxydisiloxane compound and aminoalkylalkoxyoligosiloxane compound and method for producing same | |
| WO2025188936A1 (en) | Carbo-silane functional silicones |